1

the quantity of matter or a region Properties of a system:

Thermodynamic Systems: in space upon which attention is # Intensive Properties:
concentrated in the analysis of a
problem
Everything
external to
the system
Systemand surroundings Systemand surroundings

# Extensive Properties

2
 Internal energy (U)
# State function: = Kinetic energy + Potential energy
Depends on the initial state & final state;
independent of the path used to reach from.  It’s a state function & an extensive property of

energy), H (Enthalpy) etc.

Heat and work
Example: T (Temperature), P (Pressure), U (Internal the system.
 Internal energy of a system changes when energy
is transferred into or outside the system in the
form heat or work

X Xyre = X Gyr Xyyyr −

The total energyG
of y yr Xyyyr

# Path function: a system is called its internal energy (U) –
Depends on the path between the initial & final state it changes when energy is transferred into or out of the syste
Example: W (work done), q (heat transferred) etc. 3
 State of a system
 The state of thermodynamic variables such as Work done on/by the system
pressure, temperature, volume, composition W (Work) = F (force) x w (distance moved in the direction of force)
which describes the system is called state of
the system.
 when one/more variables undergo change,
the system is said to have undergone a
change of state
• Adiabatic – no heat transferred
• Isothermal – constant temperature
• Isobaric – constant pressure
• Isochoric – constant volume

 Gas is heated  it will expand and push the piston, thereby doing work on the piston.
The work done (dw) when the system expands by dV against a pressure Pex: dw = −PexdV
X
Total work done by the system to expand from volume Vi to Vf: W = - rX dv

 This is an example of the system doing the work on the surrounding 4

 # Example 1:
 A thermodynamics process is
Thermal equilibrium of two systems with the same temperature
reversible if the process can be
 If the temperature of either system is lowered infinitesimally,
turned back such that both the
then energy flows into the system with the lower temperature.
system and the surroundings
 If the temperature of either system at thermal equilibrium is
return to their original states,
raised infinitesimally, then energy flows out of the hotter system
with no other change
anywhere else in the universe. # Example 2:
Reversible expansion:
 In reality, no such processes as Suppose a gas is confined by a piston.
reversible processes can exist. external pressure (Pex) = pressure (P) of the confined gas.
Thus, a more appropriate  Such a system is in mechanical equilibrium with its surroundings
definition is a reversible change because an infinitesimal change in the external pressure in either
in thermodynamics is direction causes changes in volume in the opposite directions.
A change that can be reversed by an dw = − X X =− X
W=−
infinitesimal modification of a variable.
dv

5
  According to 0th law:
If two systems are in thermal equilibrium with a third system,
then those two systems are in thermal equilibrium with each
other.

 Two physical systems are in thermal

equilibrium if there is no net flow of
heat (thermal energy) between
them when they are connected by a
path permeable to heat.

 The 0th law of thermodynamics defines thermal equilibrium and

forms a basis for the definition of temperature.

6
 It’s the law of conservation of energy
 The energy of an isolated system remains constant. Whenever a quantity of energy (some form)
disappears, an exactly equivalent quantity of energy (some other form) must make an appearance.

 Heat (q) and work (w) are equivalent ways of changing the internal energy of a system
 Example:
o If a weight has been raised/lowered in the surroundings, transfer of energy happens by doing the work.
o If ice has melted in the surroundings, it indicated transfer of energy as heat.

= +
 For a system, if w = work done on a system,
q = energy transferred as heat to a system &
ΔU = resulting change in internal energy
The sign of w and q:
 +ve if energy is transferred to the system as work/heat
 -ve if energy is lost from the system.
Therefore,
change in internal energy ( ) of a system = heat added to the system (q) - the work done by the system

= −
(w)
7
 If the change of a system is brought about at  Heat capacity (C) of a system b/n any two temperatures –
constant pressure, there will be change in the quantity of heat (q) required to raise the temperature
volume. of the system from the lower temperature (T1) to the
higher temperature (T2) divided by the temperature

= − (X − =
Vi = volume of initial state, Vf = volume of final state. difference.
−
X
Work done by the system,
☻ If mass of the system is 1 g,
or, ΔU = q - P (X − X )
 ΔU = q + w
the heat capacity is called the specific heat of the
− = q–P X − system
X

☻ For 1 mol of substance,
 ( + X −( +
the heat capacity is termed as ‘molar heat capacity’
X = X
 The quantity (U + PV) is called the  Molar heat capacity varies with temperature C=
enthalpy (H) of the system
 − =
 Molar heat capacity at constant volume
=
X
ΔU = ΔH – PΔV
or, ΔH = ΔU + PΔV @ constant volume w = 0 & ΔU = q
8
 Molar heat capacity at constant pressure (Cp)
ΔU = q + w

ΔU = q – P (X − X ) =
@ constant pressure,
there is change in volume As quantity (U+PV) is the 
& some work is done or, q = ΔU + pΔV enthalpy (H) of the system

 Relationship between Cp & Cv  For ideal gas, PV = RT (for 1 mole)

Δ(PV) = R ΔT
ΔH ΔU Δ(PV RΔ(T
For a system, ΔH = ΔU + Δ(PV)
+
ΔT ΔT ΔT ΔT or,
or, = = + = +R

Δ(PV or, ― =R
ΔT
or, = +

CV = 3/2 R (For monoatomic ideal gas)

CP = 5/2 R (For monoatomic ideal gas)
Heat capacity ratio, = = 5/3 for a monoatomic ideal gas
9
  Isothermal Process (constant temperature)
 In an isothermal process, the
temperature stays constant,
so the pressure and volume
work done are inversely proportional
to one another

 For an ideal gas,

The internal energy (U)  Temperature (T)
if T = fixed, ΔU = 0 (according to 1st law, which deals with ΔU)
Pressure-volume diagram As, = − =
 If the system does work, the energy comes
 q=w
from heat flowing into the system from
the surrounding
# Magnitude of w depends on whether the  if work is done on the system, heat flows
expansion is reversible or irreversible. out of the system to the surrounding.
10
 Reversible isothermal expansion:
XX
X
w= dv = dv (as PV = nRT)
(throughout the expansion, Pex = P as the expansion is reversible)
 Work done by the n moles of gas can be evaluated as:

w = − XXln = − XXln

(since = in an isothermal expansion of a perfect gas)

 The work done by a perfect gas when it
 Relations for Irreversible Isothermal expansion expands reversibly and isothermally is equal
to the area under the isotherm p = nRT/V.
a) Free expansion (expansion in vacuum)  The work done during the irreversible
w=- dv =0 expansion against the same final pressure is
a) Volume of the gas expands against a constant pressure. equal to the rectangular area shown slightly
w=- dv = -Pex (Vf – Vi) darker. Note that the reversible work done
is greater than the irreversible work done.
11
  Adiabatic process (constant heat)  Reversible adiabatic expansion
 no heat is added/ removed from a system.  Relation between T, V and P
X X
 1st law of thermodynamics: −
= =( −1
X X
ΔU = w
 ln
(as no heat is allowed to enter/leave the system, q = 0)
 Example: A gas expanding so quickly that no heat can be  ln = −1 [ X, =
transferred. Due to the expansion work, temperature
= [ X,
drops. This is exactly what happens with a carbon
dioxide fire extinguisher, with the gas coming out at high  ln ― =R

= rG
pressure and cooling as it expands at atmos. pressure
 Expansion: w = ― ve, ∆ = ― ve;
X
 ln
X
So, T of the system falls
 Work is done by the system at the expense of its  Irreversible adiabatic expansion
internal energy  Free expansion (Pex = 0) : ∆X = 0, = 0, ∆ =
 w= ∆ = (for 1 mole of 0
 ∆ =
X −X =
gas)(for 1 mole of  Expansion against a constant pressure:

−
gas) 12
  Isobaric process (constant pressure)  Isochoric process (constant volume)

 the pressure is kept constant.  the volume is kept constant

 The work done by the system in an isobaric process is  The work done is zero in an isochoric process
simply the pressure multiplied by the change in
volume  . Example of an isochoric system: A gas in a box
 Example of an isobaric system: A gas, being slowly with fixed walls
heated or cooled, confined by a piston in a cylinder.

13
 Example 1: Calculate w and ∆ for the conversion of
1 mole of water at 100 ℃ to steam at 1 atm pressure.
 Example 2: 1 mole of an ideal gas expands against

Heat of vaporisation of water at 100 ℃ is 40670 Jmol-

a constant external pressure of 1 atm from a
volume of 10 dm3 to a volume of 30 dm3. Calculate
1
the work done by the gas in Joules.
Solution:
=− X X
Solution:
P = 1 atm = 101325 Nm-2
= − (1 X 30 −
Vi = vol. of 1 mole of liquid water at 1 atm pressure

10 =− 20 X
V f = vol. of 1 mole of steam at 100 ℃ at 1 atm
= 18 ml = 18 × 10-6 m3

pressure
= (22.4 dm3 × 373)/273 = 30.60 dm3 = 0.0306 m3 R = 8.314 Jmol-1K-1 = 0.08206 dm3 atm K-1 mol-1
w = P (Vf - Vi)
= 101325 Nm-2 [0.0306 m3-(18 × 10-6 )m3] 8.314 − −

0.08206 − −
1 atm =
= 101325 Nm × 0.0306 m = 3100 Jmol
-2 3 -1

=− 20 X
Since, conversion of water to steam is accompanied Therefore,
by increase in volume, work is done by the system

= − 20
on the surroundings. 8.314 − −

0.08206 − −
Hence, w = – 3100 Jmol-1 × = – 2026 J
14
 Example 3: 1 mole of an ideal monoatomic gas at 27  C expands reversibly and adiabatically from a volume of
10 dm3 to a volume of 20 dm3. Calculate q, ∆U, W and ∆H. Given =
3
X 2
Solution:
Since the process is adiabatic, q = 0 Since for an adiabatic process, q =0,
ln = X ln
hence ΔU = w = – 1384 J
ΔH = ΔU + ΔPV = ΔU + ΔnRT
ln = ln (
3 10
 X X − X
= ΔU + nR(Tf- Ti)
2 300 20
  Tf = 189K

= =  = (1 mol) 8.314 X− − (189 − 300

X = − 923
X


∆ = ∆X
For a finite change in n moles, ΔH = – 1384 J – 923 J = – 2307 J

× 8.314 X− (189 −
3 −
=
# Note: ΔH can also be calculated by using the
2
300
= (1 mol) relation

= – 1384
 Example 4: J10 moles of an ideal gas expands reversibly and isothermally from a pressure of 10 atm to 2 atm at
300 K. Calculate the work done.
Solution: w = − XXln = −(10 mol) 8.314 X (300 ln = − 40.15
− − 10 X
2 X
15 ×
 Why we need for the 2nd law of thermodynamics?
 the 1st law uses the internal energy to identify
 The 1st law of thermodynamics does not tell us
permissible changes
anything about the direction of change. The
 the 2nd law uses the entropy to identify which of
direction of spontaneous change of a process is
these permissible changes are spontaneous.
defined by the 2nd law of thermodynamics
 A spontaneous process points towards the
 2nd law of thermodynamics direction in which the total entropy increases.
 Heat does not flow spontaneously from a cool  Entropy (S) is a state function
body to a hotter body
 Thermodynamic definition of entropy
 The entropy (S) of an isolated system increases in
the course of a spontaneous change.  The thermodynamic definition of entropy
ΔStot > 0 concentrates on the change in entropy (dS)
that occurs as the result of a physical or
Where, Stot = S + Ssur chemical process.
S = the entropy of the system of interest, &  dqrev is the energy transferred as heat
Ssur = the entropy of the surroundings reversibly to the system at the absolute
# Note: when considering applications of the 2nd law – it is a temperature T.
statement about the total entropy of the overall isolated
X= X=
system (the ‘universe’), not just about the entropy of the r X r
,
system of interest. 16
 Process that lead to an increase in entropy (ΔS > 0)  Entropy change for the system of an isothermal
expansion of a perfect gas

= −
as, wrev =― nRT ln (X /XX)
ΔU = 0, q = -w 

[from the expression of work done in a reversible

= XX (X /XX
isothermal expression]


as = X
 Δ = X (X /XX

Δ = X (X /XX

☻ Notice the increasing disorder in above processes 17

  Isothermal Reversible expansion
w = − ΔX & qrev = ΔX
 Total Entropy change in irreversible (spontaneous)
process of a perfect gas
 example: Isothermal expansion of an ideal gas at  =  +

= + −
constant temperature into vacuum
As, w = 0, = 0  = 0 [from 1st law] X X
 no heat is absorbed by =0
X
 Clausius inequality dS ≥

Hence, Δ
or removed from the surrounding,

Δ = X (X /XX = 0 , thus dS ≥ 0
=0  In an isolated system, there is no heat transfer and

A s , = +  all natural processes are spontaneous & irreversible.

= + X =0
 Reversible process:
 Δ =  +
 spontaneous in neither direction and is at equilibrium

=X this (X /XX + 0

 As Vf > XX,
> + X >0
 Irreversible process
X (X expansion
/XX
spontaneous
(irreversible) =isothermal of a
gas is accompanied by the increase in  all spontaneous process occurring in
entropy. Nature is irreversible, entropy of the
universe is increasing continuously 18
 The 1st law & the 2nd law of thermodynamics were summed up by German Physicist Rudolf Clausius as below:
The energy of the universe remains constant; the entropy of the universe tends towards a maximum
 Entropy change during different processes  Heat engine
 Its a device which transforms heat into work
 For an ideal gas (1 mole) with variable T & V
∆ = ln + Xln
 This happens in a cyclic process
 Heat engines require a hot reservoir to supply energy
 For an ideal gas with variable P & T (QH) and a cold reservoir to take in the excess energy (QC)
∆ = ln − Xln
– QH is defined as positive, QC is defined as negative
 Carnot Cycle
 For an ideal gas in an isothermal process
∆ = Xln = − Xln  A Carnot cycle (named after the French engineer Sadi
Carnot) consists of four reversible stages in which a gas
X
 For an ideal gas in an isobaric process
∆ = ln
(the working substance) is either expanded/compressed in
X
various ways
 To demonstrate the maximum convertibility of heat into
X
 For an ideal gas in an isochoric process
∆ = ln
work

X
 The system consists of 1 mole of an ideal gas which is
subjected to four strokes
19
 Four stages of Carnot Cycle: A. 1st stroke:
Curve AB: AB: Isothermal expansion at Th
Work done by the gas
 The gas is placed in thermal contact with QH (at Th) and
undergoes reversible isothermal expansion from A to B.
 The entropy change is qh/Th ( qh = the energy supplied to the

= −
system as heat from the hot source)

= rG
B. 2nd
stroke:
Curve BC (B → C): Adiabatic expansion,
Work done by the gas
 Contact with QH is broken & the gas undergoes
reversible adiabatic expansion from B to C.
 No energy leaves the system as heat, ΔS = 0
 The expansion is carried on until the temperature of
the gas falls from Th to Tc (the temperature of Qc)

− 20
 C. 3rd stroke:
Curve CD (C → D): Isothermal compression at TC,
Work done on the gas.
 The gas is placed in contact with the cold sink (Qc) and
undergoes a reversible isothermal compression from C to D at Tc.
 Energy is released as heat to the cold sink; the entropy change of

X
the system = qc/Tc, where qc is negative.
− = = XX ln
X
D. 4th stroke:
Curve DA (D → A): Adiabatic compression
Work done on the gas
 Contact with Qc is broken and the gas undergoes
reversible adiabatic compression from D to A such
that the final temperature is Th.
 No energy enters the system as heat, so the change
in entropy is zero.

= (X − X
21
 The area enclosed by the four curves represents the net
work done by the engine in one cycle
 The total change in entropy around the cycle is the sum
of the changes in each of these four steps:
=
X
+
X
 For an ideal gas, = 0 and =−

Efficiency of a heat engine

• The thermal efficiency of a heat engine is

=1− /
X G X
ℎ X XX X Xℎ ℎXX XX y
= = =
1 − X /X
• Another statement of the 2 nd Law:
 The “engine” statement of the 2nd Law:
– It is impossible for any process to have as its sole
– it is impossible for any system to have an
result the transfer of heat from a cooler object to
efficiency of 100% ( = 1) [Kelvin’s statement]
a warmer object [Clausius’s statement]22
 These appliances can be thought of as heat
engines operating in reverse.
By doing work, heat is extracted fromthe cold
 Energy efficiency of the
reservoir and exhausted to the hot reservoir.
Carnot cycle is independent
of its working substance.
 Any cyclic process that
absorbs heat at one
temperature and rejects
heat at another
temperature and is
reversible has the energy
efficiency of a Carnot cycle.

 Thermal devices or thermal machines are one of

the applications of this cycle.
 Refrigeration, Air conditioners & Heat pumps
 The heat pumps to produce heating,
● These appliances are heat engines operating
 the refrigerators to produce cooling,
in reverse.
 the steam turbines used in the ships,
● By doing work, heat is extracted from the cold
 the combustion engines of the combustion vehicles
reservoir & exhausted to the hot reservoir
 the reaction turbines of the aircraft 23
  Thermodynamic Temperature  Free energy and the spontaneity
 Suppose an engine works reversibly  As, Δ =  +
and Δ
between a hot source at a temperature 
is a criterion for the spontaneity/feasibility of a
Th and a cold sink at a temperature Tc, process.
then it follows that  It is not always easy to know the entropy change of
both system and the surrounding
Tc = (1 −  We can express this in terms of G (the free energy
η)Th function) and thus can device a criterion of spontaneity
 Kelvin used this expression to define the
thermodynamic temperature scale in in terms of the state function of the system.
terms of the efficiency of a heat engine in  There are few assumptions:
which the hot source is at a known  Assumption no 1:
temperature and the cold sink is the object The system is in thermal equilibrium with its surroundings at
of interest. a temperature T.
 The Kelvin scale (which is a special case of  Assumption no 2:
the thermodynamic temperature scale) is Heat transfer between the system and the surrounding
currently defined by using water at its happens at constant volume
triple point as the notional hot source and  Assumption no 3:
defining that temperature as 273.16 K Heat transfer between the system and the surrounding
exactly. happens at constant pressure. 24
 Under the Assumption 1 & Assumption 2  The criterion of spontaneity in terms of Gibbs Free

Clausius inequality becomes: dS −

energy change (dG) and Helmholtz energy (dA)
X X≤0
≥0
X≤0
&

the ( = ]
[we get this by applying the 1st law &
 In an endothermic reaction:
dH > 0
 TdS ≥ dU but if such a reaction is to be spontaneous at constant
dA=dU−TdS [A = Helmholtz free energy] temperature and pressure, G must decrease.
 as dG = dH − TdS
 A=U−TS
it is possible for dG to be
negative provided that

Clausius inequality becomes: dS −

 Under the Assumption 1 & Assumption 3 the entropy of the system
X
≥ 0 increases so much that
[constant P, no additional work] TdS outweighs dH.
 TdS ≥ dH  Endothermic
reactions are
dG=dH−TdS [G = Gibbs free energy] therefore driven by
the increase of
 G=H−TS
entropy of the system
25
 In an exothermic reactions

 commonly spontaneous  At chemical equilibrium,

because dH < 0 & then dG < 0 provided TdS is not so
negative that it outweighs the decrease in enthalpy.  dG = 0
 Free energy change with temperature
and pressure:

∆X = XX ln
= XX ln

26
  Example 1: Calculate the efficiency of a  Example 3: Heat supplied to a Carnot engine is 1897.8 kJ. How

superheated steam at 300 ℃ (Th = 573 K)

certain power station operates with much useful work can be done by the engine which works
between 0 ∘C and 100 ∘C.

environment at 20 ℃ (T = 293 K).

and discharges the waste heat into the
Solution:
Tc​= 0 + 273 = 273 K, Th ​= 100 + 273 = 373 K
Solution: Tc= (1 − η)Th qh = 1897.8 kJ
 η = 1 – (Tc /Th) w = × (1 −
= 1897.8 kJ × (1 −
Theoretical efficiency (η) = 1 – (293K/573K) 273
= 0.489 373
= 48.9 % = 508.7 kJ
 Work done by the engine is 508.7 kJ
# In practice, there are other losses due to
mechanical friction and the fact that
turbines do not operate reversibly.
 Example 2: Calculate the maximum efficiency of a heat engine operating between 100 ∘C and 25 ∘C

Tc​ = 25 + 273 = 298K

Solution: = 1 – (298 K/373 K)

Th​ = 100 + 273 = 373 K

Tc= (1 − η)Th
For engines, we have = 0.201
 η = 1 – (T /T )
c h = 20.1 % 27
 Example 4: 5 mole of an ideal gas expands  Example 5: Calculate the change in entropy accompanying
reversibly from a volume of 8 dm3 to 80 the heating of 1 mole of Helium gas (assumed ideal) from
dm3 at a temperature of 27 ∘C. Calculate the a temperature of 298 K to a temperature of 1000 K at
change in entropy. constant pressure. Assume Cv =3/2 R
− =X
Δ = X (X / +X=
Solution: Solution: As

XX) = 2, X = 80 dm3, X = 8 2.5 X X

 Cp =
X ∆ = ln = 2.5 8.314 X − −
ln
1000
dm3 X
Given that
298
Δ = (5 mol) (8.314 J K-1mol-1) (80 dm3/8 dm3)
×
= 25.17 X − −
= 95.73 JK -1

 Example 6: 1 mol of an ideal gas expands reversibly from a volume of 10 dm3 and 298 K to a volume of 20 dm3
and temperature 250 K. Assuming Cv =3/2 R, calculate the entropy change for the process.

∆ = ln + Xln
Solution:

X ln X
− − 250 − −
298
= 1.5 (8.314 + (8.314 ln (20
dm3/10 dm3)
= 3.57 JK-1mol-1
28
  At T = 0, all energy of thermal motion has
been quenched and in a perfect crystal all the
atoms/ions are in a regular, uniform array.
 The localization of matter and the absence of
thermal motion suggest that such materials
also have zero entropy.
 Statistical or microscopic definition of entropy:
S = k ln W
where, S = the entropy,
k = Boltzmann constant,  When T = 0, W = 1
W = the number of microstates or  S = k lnW
the total number of ways a =0
molecular state can be distributed  if the value zero is ascribed to the entropies of elements
over the energy states for a specific in their perfect crystalline form at T = 0, then all perfect
value of total energy. crystalline compounds also have zero entropy at T = 0
 Third law of thermodynamics:
The entropy of all perfect crystalline substances is zero at T = 0. 29
 Module 1

B. Chemical Kinetics

30
 What is Chemical kinetics?

 Chemical kinetics is the branch of chemistry which deals with the study of
rates (or fastness) of chemical reactions, the factors affecting it and the
mechanism by which the reactions proceed.

The rate of a chemical reaction might depend on variables such as

 pressure,
 temperature, and
 the presence of a catalyst,

It is to be contrasted with thermodynamics, which deals with the direction in

which a process occurs but in itself tells nothing about its rate

31
 The rates of reactions
 The change in concentration of reactants or products per unit time.

 Here, the instantaneous rate of disappearance of one of the reactants

(A or B) at a given time, t (at constant volume) is −d[R]/dt. Similarly, the
rate of formation of one of the products is d[P]/dt. (Note the change in
the sign)

 The negative sign indicates that the concentration is decreasing with

time.

32
 The rates of reactions

Consider a general reaction,

A+B→C

The rate of reaction will be:

d [A] d [B] d [C ]
- =- =
dt dt dt

Consider another general reaction:

aA + bB → cC + dD
where a, b, c d are stoichiometric coefficients

The rate of reaction will be:

- 1 d [A] 1 d [B] 1 d [C ] 1 d [D]

=- = =
a dt b dt c dt d dt
33
 The rates of reactions
Sample Questions:
Write rate expressions for the following reactions:
1. NO2 (g) + CO (g) → NO (g) + CO2 (g)
2. 2HI (g) → H2 (g) + I2 (g)

Solution:

d [NO2 ] d [CO] d [NO] d [CO2 ]

1. - =- = =
dt dt dt dt

2. 1 d [HI ] d [H 2 ] d [I 2 ]
- = =
2 dt dt dt

34
 Rate laws and rate constants

 The rate law is the relationship between the rate and the concentration, which
are related by a proportionality constant k, known as rate constant.
aA + bB → cC + dD

rate = k [A]m[B]n

where m and n are order of reaction in A and B, respectively k is the rate constant.

This above equation is called the rate law of the reaction.

35
 Rate laws and rate constants

 Important points about rate laws and rate constant:

 Rate law is a result of experimental observation. You CANNOT look

at the stoichiometry of the reaction and predict the rate law (unless
the reaction is an elementary reaction).

 The rate law is not limited to reactants. It can have a product term,
For example: rate = k[A]m[B]n[C]c

 The rate constant is independent of the concentrations but depends

on the temperature.

 The units for k vary. Determine units for k by considering units for rate
and for concentration.

36
 Order of a reaction

A+B→C

For rate = k[A]m[B]n

Where, m is the order of reaction in A, n is the order of reaction in B.
m and n can be integers, fractions, negative or positive.

The overall reaction order is the sum of the exponents in the rate law.

 m=0 (Zero order k[A]0)

 m=1 (First order k[A]1)
 m=2 (Second order k[A]2)

Examples:
H2 + Cl2 → 2HCl. Rate = k[H2]0 [Cl2]0 (Zero order)
SO2Cl2(g) → SO2(g) + Cl2(g) Rate = k[SO2Cl2]1 (First order)
NO2 → 2 NO + O2 Rate = k[NO2]2 (Second order)
2NO(g) + 2H2(g) → 2N2 (g) + 2H2O (g) Rate = k[NO]2 [H2]1 (Third order)
CH3COOC2H5 + H2O  CH3COOH + C2H5OH Rate = [CH3COOC2H5]1[H2O]0 (pseudo-first-order)

37
 Integrated rate laws
Since rate laws are in differential form, we must integrate them to find out the concentration as
a function of time.
Integrated first-order rate law:
A→B
d [A]
Rate = - = k [A]
dt

Separate concentration and time terms

d [ A]
= - kdt
[A]
Integrating over the limits [A]0 to [A]t and 0 to t,
d [ A]
ò [A] = -k ò dt
d [A]
[ A ]t t

ò
[ A ]0
[ A]
= -k ò dt
0

ln[ A]t - ln[ A]0 = - kt

38
Continue….
 Integrated rate laws
ln[ A]t = - kt + ln[ A]0 Straight line equation (y = mx+c)

If we plot ln [A]t versus time, then we will get a straight line having negative
slope (-k). Rate constants can be determined from experiment by plotting data
in this manner.

39
 Integrated rate laws
Other forms:

ln
[A]t = -kt
[A]0
[A]t = e - kt
[A]0
[A]t = [A]0 e - kt
Integrated first order rate law

The exponential decay of the reactant in

a first-order reaction. The larger the rate
constant, the more rapid the decay.

40
 Integrated rate laws
Question: The variation in the partial pressure of azomethane with time was
followed at 600 K, with the results given below. Confirm that the decomposition
is first-order in azomethane, and find the rate constant at 600 K.
CH3N2CH3 (g) → CH3CH3 (g) + N2 (g)

Solution: To confirm that a reaction is first-order, plot

ln([A]t/[A]0) against time and expect a straight line. Because
the partial pressure of a gas is proportional to its
concentration, an equivalent procedure is to plot ln(p/p0)
against t.
First, convert p into ln(p/p0) and draw the graph. The plot is
straight, confirming a first-order reaction, and its slope is -
3.6 10-4.
Therefore, k = 3.6  10-4 s-1.
41
 First-order Half-life
Half-life is the time it takes for the original concentration to be reduced by half.
From above:
ln
[A]t = -kt
[A]0
æ [A]0 ö
ç ÷
è 2 ø
ln = -ktt / 2
[A]0
1
ln = -ktt / 2
2
- 0.693 = -kt t / 2
t t / 2 = 0.693 / k

It is clear from the result that the half-life of a reactant is independent of its
initial concentration for a first-order reaction. Therefore, if the concentration of A
at some arbitrary stage of the reaction is [A], then it will have fallen to 1/2[A]
after a further interval of (ln 2)/k.
42
 First-order Half-life
Another important point to note is the time constant,  (tau), the time required
for the concentration of a reactant to fall to 1/e of its initial value.
æ [A] / e ö 1
k = - lnçç 0 ÷÷ = - ln = 1
è [A]0 ø e

Thus, the time constant of a first-order reaction is the reciprocal of the rate
constant,  .

Question:
1. The half-life of a first-order reaction was found to be 10 min at a certain
temperature. What is its rate constant?

Solution: k= 0.693/600s = 0.00115s-1

43
 First-order Half-life
Question:
2. If 3.0 g of substance A decomposes for 36 minutes the mass of unreacted A
remaining is found to be 0.375 g. What is the half-life of this reaction if it follows
first-order kinetics?

Solution:
ln
[A]t = -kt
[A]0
ln
[A]t / t = -k
[A]0
0.375 g
ln
3g
k =-
36 min

k =0.0578 min-1

ln 2 0.693
t1 / 2 = = = 12 min
k 0.0578
44
 Integrated second-order rate law
A→B

d [ A]
= k [ A]
2
-
dt

d [ A]
= -kdt
[A] 2

1 1
- = kt
[A]t [A]0

Integrated zero-order rate law

A→B
d [A]
= k [A]
0
-
dt

[A]t - [A]0 = - kt
45
 Pseudo First Order Reaction
 A pseudo first-order reaction can be defined as a second-order or bimolecular
reaction that is made to behave like a first-order reaction.
 This reaction occurs when one reacting material is present in great excess or is
maintained at a constant concentration compared with the other substance.
A+B C

So, if component B is in large excess and the concentration of B is very high as

compared to that of A, the reaction is considered to be a pseudo-first-order reaction
with respect to A and if component A is in large excess and the concentration of A is very
high as compared to that of B, the reaction is considered to be pseudo-first order with
respect to B.

For example:
CH3COOC2H5 + H2O  CH3COOH + C2H5OH

Rate = k [CH3COOC2H5]

The concentration of water is very high and thus does not change much during
the course of the reaction.
46
 Temperature dependence of reaction rates
The rate constant of most reactions increases with increase in the temperature.

Ea
Arrhenius equation ln k = ln A -
RT
where, A is the pre-exponential factor and Ea is the activation energy.

 A plot of ln k against 1/T is a straight line when the reaction follows the behavior described
by the Arrhenius equation.
 The higher the activation energy, the stronger the temperature dependence of the rate
constant (i.e., the steeper the slope).
 If a reaction has zero activation energy, its rate is independent of temperature.

If we plot the graph ln k vs 1/T, we will get the value of A

from the intercept at infinite T (i.e.; 1/T=0) and the value
of Ea from the slope.

47
 Temperature dependence of reaction rates
Questions:
1. The rate of the second-order decomposition of acetaldehyde (CH 3 CHO) was
measured over the temperature range 700–1000 K, and the rate constants are reported
below. Find Ea and A.

Solution: First convert T in (103) and k into ln k. Now, plot ln k against 1/T. You will
obtain the following graph having slope = -22.7 and intercept 27.7.

Now, Ea = 22.7 × (8.3145 J K−1 mol−1) × 103 K = 189 kJ mol−1

A = e27.7 dm3 mol−1s−1 = 1.1 × 1012 dm3 mol−1 s−1

48
 Temperature dependence of reaction rates

2. The values of rate constants for a reaction are 9.51x10-9 L/mol.s and
1.10x10-5 L/mol.s at temperatures 500K and 600 K respectively. Calculate
the activation energy.

Solution: k E é1 1ù
ln 2 = - a ê - ú
k1 R ë T2 T1 û
-1
k é1 1ù
Ea = - R ln 2 ê - ú
k1 ë T2 T1 û

After substituting the given values and calculating,

Ea= 176 kJ/mol

49
Energy barrier: interpretation of Arrhenius parameters

Ea
ln k = ln A -
RT
One can rewrite the above equation as:

Ea
-
k = Ae RT

To interpret Ea, lets us consider the collision between molecules of

reactants A and B:

Collision theory:
1. The rate of a reaction is proportional to the rate of reactant collisions:
2. The reacting species must collide in an orientation that allows contact
between the atoms that will become bonded together in the product.
3. The collision must occur with adequate energy to permit mutual
penetration of the reacting species’ valence shells so that the electrons
can rearrange and form new bonds (and new chemical species).
50
 Collision theory

 But all the collision will not lead to the product. Only the molecules which
are having sufficient energy (E  Ea) can cross the energy barrier.

 The minimum energy necessary to form a product during a collision

between reactants is called the activation energy (Ea).

 The kinetic energy of reactant molecules plays an important role in a

reaction because the energy necessary to form a product is provided by a
collision of a reactant molecule with another reactant molecule.

 If the activation energy is much larger than the average kinetic energy of the
molecules, the reaction will occur slowly: Only a few fast-moving molecules
will have enough energy to react.

 If the activation energy is much smaller than the average kinetic energy of
the molecules, the fraction of molecules possessing the necessary kinetic
energy will be large; most collisions between molecules will result in
reaction, and the reaction will occur rapidly.

51
 Collision theory

 The potential energy rises to a maximum and

the cluster of atoms that corresponds to the
region close to the maximum is called the
activated complex.

 After the maximum, the potential energy falls

as the atoms rearrange in the cluster and
reaches a value characteristic of the products.

 The peak of the potential energy corresponds

to the activation energy Ea..This crucial
configuration is called the transition state of
the reaction.

 The pre-exponential factor is a measure of the A potential energy profile for

rate at which collisions occur irrespective of an exothermic reaction. The
their energy. Hence, the product of A and the height of the barrier between
exponential factor, e−Ea/RT, gives the rate of the reactants and products is
successful collisions. the activation energy of the
reaction.
52
 Collision theory

Both postulates of the collision theory of reaction rates are accommodated

in the Arrhenius equation. The frequency factor A is related to the rate at
which collisions having the correct orientation occur. The exponential term
is related to the fraction of collisions providing adequate energy to
overcome the activation barrier of the reaction.

53
 Collision theory
Quantitatively, for two reactions at the same temperature

 The reaction with the higher activation energy has the lower rate constant and the
Ea
-
slower rate. The larger value of Ea results in a smaller value for e RT
reflecting the

smaller fraction of molecules with enough energy to react.

 The reaction with the smaller Ea has a larger fraction of molecules with enough
Ea
-
energy to react. This will be reflected as a larger value of e
RT
, a larger rate constant,

and a faster rate for the reaction.

(a) As the activation energy of a reaction decreases, the number of molecules with at least this much energy increases, as shown
by the shaded areas.
(b) At a higher temperature, T2, more molecules have kinetic energies greater than Ea, as shown by the yellow shaded area. 54
 Module 1

C. Catalysis

55
 Catalysis
The science and technology of catalysis is of great significance as it affects our daily
life. Four major sectors of the world economy; petroleum and energy production,
chemicals and polymer production, food industry and pollution control, involve
catalytic processes.

56
 Definition of Catalysis
“A catalyst is a chemical entity which by virtue of its presence in a
reacting system increases or decreases the rate of the reaction, itself
remaining unchanged in chemical properties or mass at the end of a
reaction.”

The phenomenon of alteration of the rate of a reaction by a catalyst is

known catalysis.

The term catalysis, proposed in 1835 by Jöns Jakob Berzelius (1779-

1848), comes from the Greek words kata meaning down and lyein
meaning loosen.

The economic significance of the catalyst industry is enormous. The

catalytic processes contribute greater than 30-40% of global GDP. The
global catalyst market size was estimated at USD 34.0 billion in 2019 and
is expected to reach USD 35.1 billion in 2020. 57
Characteristics of Catalysts

(1) The catalyst remains unchanged (in mass and chemical

composition) in the reaction.

(2) A small quantity of the catalyst is required.

(3) The catalyst does not change the equilibrium constant but the
equilibrium approaches earlier.

58
 Catalytic reactions

Catalysts work by providing alternative mechanism involving a

different transition state of lower energy. Thereby, the activation
energy* of the catalytic reaction is lowered compared to the
uncatalyzed reaction as shown in Figure below:

Figure: Schematic diagram to illustrate the effect of catalyst on activation energy of reactions. 59
 Types of catalysis

Following are the main types of catalysis:

1. Heterogeneous catalysis

2. Homogeneous catalysis

3. Enzyme catalysis

60
1. Heterogeneous catalysis
If the catalyst is present in a different phase than the reactants is
called heterogeneous catalyst and the phenomenon is known
heterogeneous catalysis.

In heterogeneous catalysis the reactions take place at the interface of

two phases. The catalyst is, often a solid and adsorbs a liquid or a gas.
This type of catalysis is of great importance in many industrial
processes.

Figure: Schematic diagram to illustrate the heterogeneous catalysis. 61

 Examples of Heterogeneous catalyst
(a) Manufacture of ammonia by the Haber process. Iron (Fe) acts as catalyst.

N2 (g) + 3H3 (g) → 2NH3 (g)

(b) Manufacture of sulphuric acid by the Contact process. Vanadium pentoxide (V2O5)
or platinum are catalysts for the production of SO3 (g) from SO2 (g) and O2 (g).

2SO2 (g) + O2 (g) → 2SO3 (g)

(c) Catalysts used in many reactions in the petroleum and polymer industries. There
are cases of heterogeneous catalysis where a reaction in the liquid phase is
catalysed by a substance in the solid state. An example is the decomposition of
H2O2 (aqueous) by MnO2 (s).

2H2O2 (aq) → 2 H2O (l) + O2 (g)

(d) Examples of reactions in which both the reactant and the catalyst are in the
solid phase. The decomposition of KClO3 is catalysed by solid MnO2.
2 KClO3 (s) → 2KCl (s) + 3O2 (g) 62
2. Homogeneous catalysis
In a reaction, if the catalyst is present in the same phase as the
reactants, it is called a homogeneous catalyst and the phenomenon
is homogeneous catalysis. Such catalysis can take place in gaseous
reaction or reactions in solution.

These chemicals help in attaining the equilibrium more quickly by

increasing the rates of both the forward and reverse reactions to an
extent.

Figure: Schematic diagram to illustrate the homogeneous catalysis. 63

Examples of homogeneous catalysis in the gas phase

(a) Oxidation of sulphur dioxide, SO2, by oxygen to sulphur trioxide,

SO 3 , in presence of nitric oxide, NO, in the Chamber Process for
sulphuric acid manufacture.
2SO2 (g) + O2 (g) → 2SO3 (g)
here, NO acts as a catalyst.

(b) The following reaction in the gas phase is catalyzed by traces of

chlorine gas, particularly in presence of light.
2N2O (g) → 2N2 (g) + O2 (g)
In presence of light chlorine forms chlorine radicals, which react with
N2O forming the intermediate radical ClO*. The proposed mechanism
is:
Step 1: N2O (g) + Cl* (g) → N2 (g) + ClO*(g)
Step 2: 2ClO*(g) → Cl2 (g) + O2 (g) 64
Examples of homogeneous catalysis in the solution phase

(a) Hydrolysis of ester in the presence of acid and alkali:

CH3COOC2H5 (l) + H2O (l) → CH3COOH (aq) + C2H5OH (aq)

(b) Hydrolysis of sucrose (cane sugar) into glucose and fructose in

presence of minerals acids acting as catalysts:

C12H22O11 (aq) + H2O (l) → C6H12O6 (aq) + C6H12O6 (aq)

(cane sugar) (glucose) (fructose)

65
D. Enzyme catalysis
Michaelis-Menton mechanism

66
 Enzymes
 Enzymes are protein-based molecules that can process certain
chemical reactions

 These reactions occur at a localized site, called the active site, at

the rate much faster than a normal chemical reaction.

 Substrate is the molecule that fits into the active site of the
enzyme and undergoes transformation to a product.

 Example of an enzyme catalysed reaction is catalase that converts

hydrogen peroxide to water and oxygen. It is an important
enzyme protecting the cell from oxidative damage by reactive
oxygen species (ROS)

H2O2 → H2O + O2
Molecular structure of Catalase
Reaction catalysed by the enzyme, catalase

67
Mechanism of enzyme-catalyzed reactions
 Enzyme-catalyzed reactions work in a
lock and key fashion.

 The substrate uniquely fits like a key

into the active site of the enzyme,
forming a lock-key complex.

 The substrate is converted into the

product by the enzyme at the active
site.

 The product is then released from the

active site.

68
 Enzymes’ effect on the activation energy
 Enzymes lower the activation energy for reactions. The
lower the activation energy, the faster the rate of the
reactions.

 For example: the enzyme catalase reduces the activation

energy for the decomposition of hydrogen peroxide to 8 kJ
mol-1, corresponding to an acceleration of the reaction by a
factor of 1015 at 298 K.

 A generic equation for the complex formation is as follows:

E+S ES P+E

69
Michaelis-Menten equation
 Michaelis-Menten equation is a commonly used model that assumes that the concentration of the enzyme
remains constant.

 The enzyme reacts with the substrate for form an enzyme-substrate complex, which leads to the synthesis of the
product and the release of the enzyme

ka kb
E+S ES P+E
ka’

 Where, ka is the rate of formation of ES, ka’ is the rate of dissociation of ES, and kb is the rate of formation of
P from ES.

70
Michaelis-Menten Mechanism
One of the earliest descriptions of the action of enzymes is the Michaelis-Menten mechanism. The proposed
mechanism, with all species in an aqueous environment, is as follows.

Step 1: The bimolecular formation of a combination, ES, of the enzyme E and the substrate S:
E + S → ES Rate of formation of ES = ka[E][S]

Step 2: Unimolecular decomposition of the complex:

ES → E + S Rate of decomposition of ES = ka’[ES]

Step 3: The unimolecular formation of products P and the release of the enzyme from its combination
with the substrate:
ES → P + E Rate of decomposition of ES = ka’[ES]
Rate of decomposition of ES = ka’[ES]

71
Derivation
Since the product P is formed irreversibly, according to the rate law, the rate of formation of the product P is

Rate of formation of P = kb[ES]

Since the net rate of formation of [ES] is zero, we can write the following:

Net rate of formation of ES = ka[E][S] - ka’[ES] - kb[ES] = 0

G [ ][ ]
[ ]=
G +G
So,

However, [E] and [S] are the molar concentrations of the free enzyme and free substrate. If [E]0 is the total
concentration of enzyme, then [E] + [ES] = [E]0 and we can replace [E] in this expression by [E]0 − [ES].
Therefore,
G ([ ] − [ ] [ ]
[ ]=
G +G

72
 Derivation
Multiplication by (ka′+kb) gives first G [ ]+G [ ]=G [ ] [ ]−G [ ][ ]

And then, (G + G + G [ ] [ ]=G [ ] [ ]

G +G
+[ ] [ ]=[ ] [ ]
+G
Division by ka turns this expression into

We recognize the first term inside the parentheses as KM, so this expression rearranges to

[ ] [ ]
[ ]=
[ ]+
{1.
1}

Where KM is the Michaelis constant (having the dimension of concentration), so

G +G
=
+G
{1.
2}
73
Derivation
The rate law for the rate of formation of product in terms of the concentrations of enzyme and substrate turns out
to be
Rate of formation of P = kb[ES] = kr[ES]0

G [ ]
G =
[ ]+
So, from 1.1, we can say that, {1.
3}

According to eqn 1.3, the rate of enzymolysis is first-order in the added enzyme concentration, but the effective
rate constant k depends on the concentration of substrate. We can infer from eqn 1.3 that:

 When [S] << KM, the effective rate constant is equal to kb[S]/KM. Therefore, the rate increases linearly with [S]
at low concentrations.
 When [S] >> KM, the effective rate constant is equal to kb, and the rate law in eqn 1.3 reduces to

Rate of formation of P = kb[E]0

74
Conditions for maximum and minimum
velocities
 When [S] << KM, the effective rate constant is equal to
kb[S]/KM. Therefore, the rate increases linearly with [S] at low
concentrations.

 When [S] >> KM, the effective rate constant is equal to kb,
and the rate law in eqn 1.3 reduces to

Rate of formation of P = kb[E]0

75
Maximum velocity-Vmax
When [S] >> KM, the rate is independent of the concentration of S because there is so much substrate present that
it remains at effectively the same concentration even though products are being formed.

Under these conditions, the rate of formation of product is a maximum, and kb[E]0 is called the maximum velocity,
vmax, of the enzymolysis:
=G [ ] {1.
4}
The rate-determining step is Step 3: the decomposition of ES to form P, because there is ample ES present
(because S is so abundant), and the rate is determined by the rate at which ES reacts to form the product.

It follows from eqns 1.1 and 1.4 that the reaction rate v at a general substrate composition is related to the
maximum velocity by

[ ]
=
[ ]+
{1.
5}

76
Lineweaver-Burk Plot
If we take the reciprocal on both sides of eqn 1.5, it becomes,

1 [ ]+ 1 1
= = +
[ ] [ ]

Since this expression has the form,

1 1 1
= + X
[ ]
{1.
6}
y intercept slope x

Eqn. 1.6 is the basis for the analysis of enzyme kinetic data using a Lineweaver-Burk Plot, a graph of 1/v
(the reciprocal of the reaction rate) against 1/[S] (the reciprocal of the substrate concentration).

77
Lineweaver-Burk Plot
 The intercept of the extrapolated (dotted) straight line with the
horizontal axis is used to obtain the Michaelis constant, KM.
 The intercept with the vertical axis, is used to determine vmax = kb[E]0,
and hence kb. The slope may also be used, as it is equal to KM /vmax
 Alternatively, note that the extrapolated intercept with the
horizontal axis (where 1/v = 0) occurs at 1/[S] = −1/KM.

78
Catalytic constant & efficiency
The turnover frequency, or catalytic constant, of an enzyme, kcat, is the number of catalytic cycles (turnovers)
performed by the active site in a given interval divided by the duration of the interval.

This quantity has units of a first-order rate constant and, in terms of the Michaelis–Menten mechanism, is
numerically equivalent to kb, the rate constant for release of product from the enzyme–substrate complex. So, it
follows that,

G =G =
[ ]
{1.
7}

The catalytic efficiency, η (eta), of an enzyme is the ratio kcat /KM. The higher the value of η, the more efficient is
the enzyme. We can think of the catalytic activity as the effective rate constant of the enzymatic reaction.

G G G
η= =
G +G
{1.
8}

The efficiency reaches its maximum value of ka when kb >> ka ′.

79
Sample problem
The enzyme carbonic anhydrase catalyzes the hydration of CO2 in red blood cells to give bicarbonate (hydrogen
carbonate) ion:
CO2(g) + H2O(l) → HCO3-(aq) + H+(aq)

The following data were obtained for the reaction at pH=7.1, 273.5 K and an enzyme concentration of 2.3 nmol
dm-3

[CO2]/(mmol dm-3) v/(mmol dm-3s-1)

1.25 2.78x10-2
2.5 5.00x10-2
5 8.33x10-2
20 1.67x10-1

Determine the catalytic efficiency of carbonic anhydrase at 273.5 K

80
Contd.
We construct a Lineweaver-Burk plot by drawing a table of 1/[S] and 1][v]. The intercept at 1/[S]=0 is vmax and
the slope of the line through the points is KM/vmax. So, KM is found from the slope divided by the intercept. From
eqn 1.7, and the enzyme concentration, we calculate kcat and the catalytic efficiency from eqn 1.8

1/[CO2]/(mmol dm-3) 1/v/(mmol dm-3s-1)

0.8 35.97
0.4 20.00
0.2 12.00
0.05 5.99

From the graph, slope is 40 and intercept is 4.

81
Contd.

82